JP2004115783A - Paste for use in partition, and method for manufacturing plasma display panel - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a paste for use in partitions which causes few cracks at the time of drying even if the thickness of a coating film is increased and which can keep good the adhesion between the film dried and a dry film without extending a time required for sandblasting. <P>SOLUTION: The paste for use in the partitions is such that the paste comprises a glass powder, resins and an organic solvent and moreover the above resins comprise polyvinyl butyral and/or a polymethacrylate. Similarly, the paste for use in the partitions is such that the paste comprises a glass powder, a resin, an organic solvent and a surfactant and moreover the above resin comprises an acrylic polymer and preferably, the resin comprises ethyl cellulose in addition. <P>COPYRIGHT: (C)2004,JPO

Description

The present invention relates to a paste used for forming a partition wall of a plasma display panel (PDP), a fluorescent display tube (VFD) or the like.

One of the features of the PDP or VFD panel structure, which is a thin flat color display device, is a partition wall formed at equal intervals over the entire screen to divide pixels. For example, in a PDP, a transparent electrode and a dielectric layer that covers the transparent electrode are usually formed on the surface of the front glass substrate, and the dielectric layer is covered and protected with an MgO film. Usually, an address electrode and an insulating coating layer that covers the address electrode are formed on the surface of the rear glass substrate, and a partition wall is formed on the insulating coating layer.

The partition walls are formed in a lattice pattern at equal intervals over the entire screen, and the lattice interval is typically 200 to 300 μm. The width and height of the partition walls are typically 80 μm and 150 μm, respectively.

The partition walls of the PDP are formed as follows, for example.
First, a paste is prepared by mixing an inorganic powder made of a ceramic filler for maintaining a partition shape, glass powder as a fixing material, a heat-resistant pigment for color tone adjustment, and the like with a vehicle.

Usually, PbO—SiO ₂ —B ₂ O ₃ glass powder is used as the glass powder, white pigment such as titania or black pigment such as Cr—Cu composite oxide is used as the heat resistant pigment, and alumina or zircon as the ceramic filler. , Powders such as zirconia are used. The typical composition of the PbO—SiO ₂ —B ₂ O ₃ glass in terms of mol% is B ₂ O ₃ 15%, SiO ₂ 40%, PbO 35%, Al ₂ O ₃ 5%, TiO _2. 5%. The vehicle includes a resin and an organic solvent. Ethyl cellulose or the like is used for the resin, and terpineol or the like is used for the organic solvent (see, for example, Patent Document 1).

The partition wall paste thus obtained is applied to the entire surface of the glass substrate on which the address electrode and the insulating coating layer covering the address electrode are formed, and dried. Next, a dry film resist is laminated on the dried coating layer, an exposure mask having a desired partition pattern is set, and after exposure, developed using an aqueous sodium carbonate solution or the like, the partition is formed on the coating layer. Form a pattern.

Unnecessary portions of the coating layer on which the partition pattern is formed are cut by sandblasting to obtain an unfired partition. The dry film remaining on the unfired partition walls is removed with an aqueous sodium hydroxide solution, ethanolamine or the like, and then fired at 500 to 620 ° C. to form partition walls on the glass substrate.
JP 2001-106547 A (page 3)

At present, various attempts have been made to improve the image quality of PDPs, and one of them is to increase the brightness.
In order to achieve high brightness, it is effective to increase the height of the partition wall for the purpose of increasing the amount of ultraviolet light emission by expanding the plasma discharge region and increasing the coating area of the phosphor.

When the partition wall is formed by the sand blasting method using the conventional partition wall paste as described above, the coating film thickness increases when the partition wall height is increased. There are problems such as long time. If there is a crack on the dry film, the crack may be a defect of the formed partition wall.

Also, if the amount of paste resin is reduced to shorten the time required for sand blasting, the time required for sand blasting will be shortened, but the adhesion between the dry film and the dry film will be weak, and the dry film will easily peel off from the dry film during sand blasting. There is a problem.

The present invention provides a partition wall paste that is less likely to crack during drying even when the coating thickness is increased, and that can maintain good adhesion between the dried film and the dried film without increasing the time required for sandblasting. Objective.

The present invention provides a partition wall paste containing glass powder, a resin and an organic solvent, and includes a partition wall paste containing polyvinyl butyral and / or polymethacrylate as a resin (hereinafter referred to as paste 1 of the present invention). ). Moreover, what contains surfactant in the paste 1 of this invention is provided.
The present invention also provides a partition wall paste containing glass powder, a resin, an organic solvent, and a surfactant, the partition wall paste containing an acrylic polymer as a resin (hereinafter referred to as paste 2 of the present invention). .)

Since the paste 1 of the present invention uses polyvinyl butyral or polymethacrylate, even if the coating film thickness is increased, cracks are unlikely to occur during drying, the time required for sandblasting does not increase, and the dry film and the dry film Good adhesion can be maintained.
In addition, by using a surfactant, it is possible to prevent solidification of the dry film and deterioration of the adhesion between the dry film and the substrate, and further reduce the time required for sandblasting, and the adhesion between the dry film and the dry film. Can be maintained well. The shortening of the time required for sand blasting is presumed that the surfactant adsorbs to inorganic powder such as glass powder in the partition wall paste and weakens the bond between the resin and the inorganic powder, so that the resin is likely to fly during sand blasting. doing.

The present invention is a method for manufacturing a plasma display panel having a back substrate, the step of applying the partition wall paste on the glass substrate of the back substrate, drying, processing, and firing to form the partition wall A method of manufacturing a plasma display panel having the above is provided. According to this manufacturing method, a PDP having a high partition wall, high brightness, and high image quality can be manufactured without particularly increasing the time required for sandblasting.

According to the present invention, even when the coating film thickness is increased, cracks are hardly generated during drying, the time required for sandblasting is not prolonged, and a partition wall paste having good adhesion to the dry film can be obtained. In addition, according to the present invention, a PDP having high brightness and excellent image quality can be produced without particularly increasing the time required for sandblasting.

The partition wall paste of the present invention (hereinafter referred to as the paste of the present invention) usually comprises an inorganic powder such as a glass powder, a ceramic filler, and a heat-resistant pigment, and a vehicle containing a resin as an organic binder and a solvent for dissolving the resin. Manufactured by kneading.
The paste of the present invention is used for forming barrier ribs such as PDP and VFD, and is usually applied to the entire surface of a glass substrate on which an address electrode and an insulating coating layer for covering the address electrode are formed. After being processed into a desired shape by a method or the like, it is fired.

The temperature at which the firing is performed is usually 500 to 620 ° C. If the temperature is lower than 500 ° C., a part of the resin remains in the partition after firing, and the residual resin may be released as a gas when sealing the panel in PDP or VFD or during panel discharge. If it exceeds 620 ° C., the glass substrate may be deformed.

The softening point T _S of the glass powder is preferably 450 to 650 ° C. If it is less than 450 degreeC, glass may flow too much at the time of the said baking, and there exists a possibility that a predetermined partition shape may not be obtained. More preferably, it is 500 degreeC or more. If it exceeds 650 ° C., the glass fluidity at the time of firing is lowered, and there is a possibility that dense partition walls cannot be obtained. More preferably, it is 620 degreeC or less, Especially preferably, it is less than 600 degreeC.

The average linear thermal expansion coefficient α at 50 to 350 ° C. of the fired body obtained by firing the glass powder is preferably 65 × 10 ^{−7 to} 85 × 10 ⁻⁷ / ° C. Outside this range, expansion matching with the glass substrate becomes difficult. More preferably, it is 70 × 10 ⁻⁷ to 80 × 10 ⁻⁷ / ° C. The average linear expansion coefficient of the glass substrate is typically 65 × 10 ^{−7 to} 85 × 10 ⁻⁷ / ° C.

Glass powder is essentially expressed in terms of mol% based on the following oxides:
_{B 2 O 3 5~80%, SiO} 2 0~45%, 0~60% ZnO, PbO + Bi 2 O 3 0~70%, MgO + CaO + SrO + BaO 0~50%, Li 2 O + Na 2 O + K 2 O 0~30%, Al ₂ O ₃ + TiO ₂ + ZrO ₂ 0-13%, CuO 0-3%, SnO ₂ 0-3%, or
B ₂ O ₃ 0-60%, SiO ₂ 20-65%, ZnO 0-60%, PbO + Bi ₂ O ₃ 0-70%, MgO + CaO + SrO + BaO 0-50%, Li ₂ O + Na ₂ O + K ₂ O 0-30%, Al ₂ O ₃ + TiO ₂ + ZrO ₂ 0-13%, CuO + SnO ₂ + CeO ₂ 0-5%,
Preferably it consists of. Here, for example, “SnO ₂ : 0 to 3%” means that SnO ₂ is not essential but may be contained up to 3%.

In addition to the above components, the glass powder may contain other components as long as the object of the present invention is not impaired. In that case, the total content of “other components” is preferably 5% or less.
As the “other components”, rare earth oxides such as La ₂ O ₃ , P ₂ O ₅ , MnO, Fe ₂ O ₃ , CoO, NiO, GeO ₂ , Y ₂ O ₃ , MoO ₃ , Rh ₂ O ₃ , Examples thereof include Ag ₂ O, In ₂ O ₃ , TeO ₂ , WO ₃ , ReO ₂ , V ₂ O ₅ , and PdO.

セ ラ ミ ッ ク ス Ceramic filler is not essential, but may be contained if necessary. Examples of the ceramic filler include powders of alumina, mullite, zircon, zirconia, cordierite, aluminum titanate, β-spodumene, α-quartz, quartz glass, β-quartz solid solution, β-eucryptite, and the like.

Although the heat resistant pigment is not essential, it may be contained if necessary. Examples of the heat resistant pigment include white pigments such as titania, pigments such as Fe—Mn complex oxide, Fe—Co—Cr complex oxide, and Fe—Mn—Al complex oxide.

The content ratio of the resin in the paste of the present invention is preferably 0.5 to 8 parts by mass with 100 parts by mass of the inorganic powder. If it is less than 0.5 mass part, there exists a possibility that adhesiveness with a dry film may become weak. More preferably, it is 1 part by mass or more. If it exceeds 8 parts by mass, the blast rate may be too slow. More preferably, it is 4 parts by mass or less or 3 parts by mass or less.

The resin of the paste 1 of the present invention is one of polyvinyl butyral and polymethacrylate in order that the time required for sandblasting does not become long and the adhesion to the dry film is good when the coating film thickness is increased. Must contain one or more resins.

The weight average molecular weight of polyvinyl butyral is preferably 20,000 to 130,000. If it is less than 20,000, the adhesion between the dry film and the dry film may be insufficient. If it exceeds 130,000, it becomes difficult to dissolve in an organic solvent such as terpineol.

The weight average molecular weight of the polymethacrylate is preferably 10,000 to 800,000. If it is less than 10,000, there exists a possibility that the adhesiveness of a dry film and a dry film may be insufficient. More preferably, it is 50,000 or more. If it exceeds 800,000, it becomes difficult to dissolve in an organic solvent such as terpineol. More preferably, it is 360,000 or less.

The resin of the paste 2 of the present invention does not contain an acrylic polymer so that the time required for sandblasting does not become long and the adhesion to the dry film is good when the coating film thickness is increased. Don't be.

The weight average molecular weight of the acrylic polymer is preferably 10,000 to 800,000, and more preferably 50,000 to 360,000. If it is less than 10,000, there exists a possibility that the adhesiveness of a dry film and a dry film may be insufficient. If it exceeds 800,000, it becomes difficult to dissolve in an organic solvent such as terpineol.

The acrylic polymer preferably has 75 to 100% by mass of at least one selected from the following formulas 1 to 4 as a repeating unit. More preferably, the acrylic polymer is polymethacrylate containing 75 to 100% by mass of Formula 1 or Formula 3 as a repeating unit.
- (CH ₂ -CHCOOH) - ··· Formula 1,
_{- (CH 2 -CCH 3 COOH)} - ··· Formula 2,
- (CH ₂ -CHCOOR) - ··· Formula 3,
_{- (CH 2 -CCH 3 COOR)} - ··· Equation 4.
Here, R is a methyl group, an ethyl group, an n-propyl group, an n-butyl group, an i-butyl group, a hexyl group, a 2-ethylhexyl group, or C _n H _{2n + 1} (n: 10 to 18).

This acrylic polymer is obtained by (co) polymerizing 75 to 100% by mass of at least one monomer selected from the following formulas 1 ′ to 4 ′ and 0 to 25% by mass of other monomers. Can do. The polymerization method is not particularly limited.
CH ₂ = CHCOOH Formula 1 ′,
CH ₂ = CCH ₃ COOH Formula 2 ′,
CH ₂ = CHCOOR Formula 3 ′,
CH ₂ = CCH ₃ COOR Formula 4 ′.
Here, R is as defined in formulas 3 and 4.

If these resins are not contained, the time required for sandblasting may be increased, or the dry film may be peeled off during sandblasting.

Although it is not essential as a resin, it is preferable to contain ethyl cellulose. If ethyl cellulose is not contained, problems such as difficulty in coating, difficulty in ensuring the smoothness of the dry film, and the tendency for dry film cracking to occur may occur.

The weight average molecular weight of ethyl cellulose is preferably 50,000 to 200,000. If it is less than 50,000, the adhesion between the dry film and the dry film may be insufficient. If it exceeds 200,000, it becomes difficult to dissolve in an organic solvent such as terpineol.

When the resin contains ethyl cellulose, the content ratio of ethyl cellulose is preferably 95 parts by mass or less with respect to 100 parts by mass of the resin. When the said content rate exceeds 95 mass parts, it will become difficult to ensure the adhesiveness of a dry film, ensuring sufficient blast rate.
In the paste 1 of this invention, when resin contains ethyl cellulose, it is preferable to contain 20-90 mass parts of ethyl cellulose and polyvinyl butyral and / or polymethacrylate in the ratio of 10-80 mass parts in total. It is more preferable to contain 20 to 80 parts by mass of ethyl cellulose and 20 to 80 parts by mass of polyvinyl butyral and / or polymethacrylate in total. Particularly preferably, ethyl cellulose is 40 parts by mass or more, most preferably 50 to 70 parts by mass of ethyl cellulose, a ratio of 30 to 50 parts by mass in total of polyvinyl butyral and / or polymethacrylate, or 50 to 85 parts by mass of ethyl cellulose. , Polyvinyl butyral and / or polymethacrylate in a total proportion of 15 to 50 parts by mass.
In the paste 2 of this invention, when resin contains ethyl cellulose, it is preferable to contain ethyl cellulose 25-90 mass parts and an acrylic polymer in the ratio of 10-75 mass parts. The ethyl cellulose is more preferably 40 parts by mass or more, particularly preferably 50 parts by mass or more.
The resin in the present invention consists essentially of a thermoplastic resin, but may contain a resin other than the thermoplastic resin as long as the object of the present invention is not impaired.

Organic solvents include terpineol, ethylene glycol alkyl ether (eg, ethylene glycol monoethyl ether), diethylene glycol monoalkyl ether (eg, butyl carbitol), ethylene glycol monoalkyl ether acetate (eg, butyl carbitol acetate), diethylene glycol monoalkyl ether acetate, Diethylene glycol dialkyl ether acetate, triethylene glycol alkyl ether acetate, triethylene glycol alkyl ether, propylene glycol alkyl ether, propylene glycol phenyl ether, dipropylene glycol alkyl ether, tripropylene glycol alkyl ether (for example, tripropylene glycol n-butyl ether) ), Propylene glycol alkyl ether acetate, dipropylene glycol alkyl ether acetate, tripropylene glycol alkyl ether acetate, acetyl trialkyl citrate, trialkyl citrate, 2,2,4-trimethyl-1,3 pentadiol monoisobutyrate 2,2,4-trimethyl-1,3 pentadiol diisobutyrate, dimethyl phthalate (dimethyl phthalate), diethyl phthalate (diethyl phthalate), and dibutyl phthalate (dibutyl phthalate), where alkyl is methyl, It is preferably at least one selected from the group consisting of ethyl, propyl, butyl, hexyl or 2-ethylhexyl). More preferably, it is at least one selected from the group consisting of terpineol, diethylene glycol monobutyl ether, 2,2,4-trimethyl-1,3 pentadiol monoisobutyrate and propylene glycol phenyl ether.

The surfactant is not essential in the paste 1 of the present invention, but may be contained as necessary. Phosphate ester, carboxylic ester, polyalkyl glycol ether, alkyl polyether amine, alkyl Examples thereof include ammonium salts.

The surfactant in the paste of the present invention preferably has a polar group in the hydrophilic part. Examples of the polar group include one or more polar groups selected from the group consisting of a carboxyl group, a phosphate group, an amino group, and a hydroxyl group. Among these surfactants having a polar group, carboxylic acid or phosphate ester of polyoxyalkylene alkyl ether represented by the following formula 5 or salt thereof, alkyl phosphate ester or salt thereof, hydroxyethylalkylamine, poly An oxyalkylene alkylamine or an alkylolamine salt of polyester is preferred. Here, alkyl is a linear or branched alkyl having 8 to 20 carbon atoms (for example, octyl, lauryl, cetyl, stearyl, oleyl, etc.), and alkylene is a linear or branched alkyl having 2 to 5 carbon atoms. Alkylene (for example, ethylene, propylene, etc.).

R ₁ O (R ₂ O) _n X Formula 5
Here, R ₁ is a linear or branched alkyl group having 8 to 20 carbon atoms, R ₂ is an alkylene group having 2 to 5 carbon atoms, n is 1 to 20, and X is a carboxyl group or a phosphate group.

Specifically, polyoxyethylene lauryl ether carboxylate, polyoxyethylene lauryl ether phosphate, etc. as the compound represented by the formula 5, lauryl phosphate, etc. as alkyl phosphate, N as hydroxyethylalkylamine, etc. Examples of polyoxyalkylene alkylamines such as -hydroxyethyl laurylamine include polyoxyethylene laurylamine.

By containing a surfactant, as described above, it is possible to prevent cracking of the dried film and a decrease in adhesion between the dried film and the substrate, further reducing the time required for sandblasting, It is possible to maintain good adhesion.
Two or more kinds of surfactants may be contained in the paste of the present invention. The content of the surfactant in the paste of the present invention is preferably 0.01 to 3% by mass. 2 mass% or less is more preferable, and 1 mass% or less is especially preferable. If it exceeds 3% by mass, cracks may occur in the dry film, and the adhesion between the dry film and the substrate may be deteriorated.

The paste of the present invention preferably contains a nonionic surfactant when viscosity adjustment or the like is desired. In this case, the total content of nonionic surfactants is preferably 3% by mass or less.
Nonionic surfactants include polyethylene glycol alkyl ether, polyethylene glycol alkyl ester, polyoxyethylene alkyl ether, polyoxyethylene alkyl ester, polyoxyethylene polypropylene alkyl ether, polyethylene glycol alkylamine, hydroxyethyl alkylamine, phosphoric acid Examples thereof include esters, carboxylic acid esters, polyalkyl glycol ethers, alkyl polyether amines, and alkyl ammonium salts. Here, alkyl is octyl, lauryl, cetyl, stearyl, oleyl and the like.

It is also preferable to include the following viscosity ratio reducing agent in the paste of the present invention because the time required for sandblasting can be shortened while maintaining good adhesion to the dry film.
Here, in the present invention, the viscosity of the paste is measured with a rotational viscometer, the viscosity measured with a spindle speed of 10 rpm (corresponding to a shear rate of 4 s ⁻¹ ) is η ₁₀ , and the spindle speed is 50 rpm ( Η ₁₀ / η ₅₀ is defined as the viscosity ratio, where η ₅₀ is the viscosity measured as shear rate = 20 s ⁻¹ .
The viscosity ratio reducing agent is such that when 5 parts by mass is added to 100 parts by mass of the paste, the viscosity ratio of the paste before addition is 1, and the viscosity ratio of the paste after addition is 0.9 or less. . The viscosity ratio after addition is preferably 0.8 or less.
The boiling point or decomposition point of the viscosity ratio reducing agent is preferably 600 ° C. or lower, and the boiling point is typically 300 ° C. or higher.
Surfactants are typical as viscosity ratio reducing agents.

Below, the manufacturing method of PDP using the paste of this invention is demonstrated.
In the present invention, the PDP is manufactured as follows, for example, in the case of an AC system.
As shown in FIG. 1, an electrode 2 is formed by patterning on a front glass substrate 1a to form a bus line (not shown), and then a transparent dielectric layer 3 that protects the electrode is formed and transparent. A protective film usually made of MgO is formed on the dielectric layer 3 to manufacture a front substrate.
On the other hand, in the production of the rear substrate, first, the patterned address electrode 5 is formed on the rear glass substrate 1b, and then the insulating coating layer 8 that covers the address electrode is formed. As described above, the partition wall 6 is formed by applying the paste of the present invention on the entire surface of the insulating coating layer 8 and drying it, processing it into a desired partition pattern by sandblasting, and baking it. Next, the phosphor layer 4 is formed by printing and baking.
In the PDP, a sealant (not shown) is applied to the periphery of the front glass substrate 1a and the rear glass substrate 1b with a dispenser, and the front substrate and the rear substrate manufactured as described above are assembled so that the electrodes of the substrate face each other. A panel is formed, fired, the inside of the plasma display is exhausted, and a discharge gas such as Ne or He—Xe is sealed in the discharge space 7.
In the above example, the AC method is described, but the present invention can also be applied to a DC method.

The composition represented by mol% is B ₂ O ₃ : 37.1%, SiO ₂ : 24.8%, PbO: 24.7%, BaO: 8.9%, Al ₂ O ₃ : 3.5%, SnO ₂ : 1% glass powder A and B ₂ O ₃ : 37.1%, SiO ₂ : 24.7%, ZnO: 3.5%, PbO: 25.7%, BaO: 4.5% _{, Al 2 O 3: 3.5%} , SnO 2: was prepared by the glass powder B is 1% as follows.

That is, the raw materials were prepared and mixed so as to have the above composition, melted for 1 hour using a platinum crucible in an electric furnace at 1200 to 1350 ° C., and the molten glass was poured out and formed into a sheet glass. The thin glass sheet was pulverized with a ball mill to obtain a glass powder having an average particle size of 1.5 μm. As the glass powder, glass powder A was used in Examples 1, 2, 4 to 6, and glass powder B was used in Examples 3 and 7 to 12, respectively.

Next, each vehicle was stirred and dissolved at 85 ° C. for 4 hours with the constitution shown in Tables 1 to 3 for the resin and the organic solvent. The main component of polymethacrylate is isobutyl methacrylate and contains 99% by mass of isobutyl methacrylate as a repeating unit.
In Tables 1 to 3, the molecular weight is the weight average molecular weight, and the amount of resin in the vehicle is the resin content when the vehicle is 100 parts by mass. Solvent 1 is terpineol, solvent 2 is diethylene glycol monobutyl ether, solvent 3 is 2,2,4-trimethyl-1,3 pentadiol monoisobutyrate, and solvent 4 is propylene glycol phenyl ether.

Next, an inorganic powder was prepared by mixing glass powder, alumina powder, silica powder and titania powder in the ratios shown in Tables 1 to 3 by mass ratio.
As for the paste, the resin content ratio in the vehicle with respect to 100 parts by mass of the inorganic powder in the pastes having the respective configurations shown in Tables 1 to 3 is indicated in parts by mass in the column of “resin content of paste” in the same table. The vehicle and the inorganic powder were mixed at a proper ratio.

The paste was prepared as follows. That is, 100 parts by mass of the paste to be produced is added to the inorganic powder and vehicle, and the surfactant shown in Tables 1 to 3 is added in a proportion of 0 to 1.0 part by mass, and the mixture is kneaded with three rolls and the shear rate is 4 s. The viscosity was adjusted so that the viscosity at ^-1 was 40 Pa · s, and a paste was prepared.
Surfactant 1 is N-hydroxyethyllaurylamine (a compound having a structure represented by the following formula (1)), and surfactant 2 is an alkylolamine salt of a copolymer containing a phosphate group, and “Disperbyk180”. (Bick Chemie Japan Co., Ltd.) was used.

The obtained paste was blade-coated with a 400 μm spacer on a 10 cm square glass substrate (PD200 manufactured by Asahi Glass Co., Ltd.) and dried in a 120 ° C. dryer for 1.5 hours to obtain a dry film. Examples 1 to 11 are the present invention, and Example 12 is a comparative example.

As a result of visual observation of the obtained dry film, no crack was observed in any of Examples 1 to 12.

Next, the dry films of Examples 1 to 12 were examined for the blast rate (unit: μm / time) and the dry film cumulative peel number (unit: book), which is an index of dry film adhesion, as described below. A result is shown in the column of the blast rate and peeling number of Tables 1-3.

Blast straight: Drying using a sand blasting device (model SCM-1ADE-NH-401P) manufactured by Fuji Seisakusho under the conditions of suction pressure 150 kPa, pumping air pressure 75 kPa, gun moving speed 4 m / min, and roller rotation speed 2.5 rpm. The film was blasted 4 times or less, and the value of the gradient approximated linearly by taking the number of blasts on the horizontal axis and the cumulative cutting depth on the vertical axis was taken as the blast rate. In addition, about the frequency | count of blasting, when it cut all by less than 4 times, it was set as the frequency | count that cutting was completed. For example, when cutting is completed in 3 times, the number of blasts is 3 times.

Cumulative number of dry films peeled: Cut dry film BF704 made by Tokyo Ohka Kogyo Co., Ltd. into 4 cm x 5 cm, and pass through a laminator once under the conditions of a roll temperature of 110 ° C, a roll pressure of 150 kPa, and a substrate transport speed of 0.45 m / min. did. Thereafter, an exposure mask having a pattern with a total of 40 lines of 8 types of line widths of 40, 50, 60, 80, 100, 125, 150, and 200 μm is set and exposed at 250 mJ / cm ^2. Developed with a 3% aqueous solution of sodium carbonate and dried for 15 minutes in a dryer at 50 ° C. Using a sandblasting device (model SCM-1ADE-NH-401P) manufactured by Fuji Seisakusho, the suction pressure was 450 kPa, the pumping air pressure was 225 kPa, the gun moving speed was 2.7 m / min, and the roller rotation speed was 6.25 rpm. The number of lines in which the dry film was peeled off by half or more of the line length was defined as the cumulative number of peeled films.

It is preferable that the blast rate is 30 μm / time or more. If it is less than 30 μm / time, it may take too much time to sandblast a thick dry film. More preferably, it is 35 μm / time or more. More preferably, it is 40 μm / time or more, and particularly preferably 50 μm / time or more.

The cumulative number of peeled dry films is preferably less than 25 in total. When the number is 25 or more, the dry film may be peeled off from the dried film even under the sand blasting condition at the time of partition formation, which is usually performed under conditions milder than the sand blasting condition. More preferably, it is less than 20, and particularly preferably less than 15.

It is a schematic sectional drawing of a typical example of a plasma display.

Explanation of symbols

DESCRIPTION OF SYMBOLS 1a: Front glass substrate 1b: Back glass substrate 2: Electrode 3: Transparent dielectric layer 4: Phosphor layer 5: Address electrode 6: Partition 7: Discharge space 8: Insulation coating layer

Claims (16)

A partition wall paste containing glass powder, a resin and an organic solvent, wherein the partition wall paste contains polyvinyl butyral and / or polymethacrylate as the resin. The partition wall paste according to claim 1, further comprising a surfactant. A partition wall paste containing glass powder, a resin, an organic solvent, and a surfactant, wherein the partition wall paste contains an acrylic polymer as a resin. The acrylic polymer has 75 to 100% by mass of at least one selected from the following formulas 1 to 4 as a repeating unit.
- (CH ₂ -CHCOOH) - ··· Formula 1,
_{- (CH 2 -CCH 3 COOH)} - ··· Formula 2,
- (CH ₂ -CHCOOR) - ··· Formula 3,
_{- (CH 2 -CCH 3 COOR)} - ··· Equation 4.
Here, R is a methyl group, an ethyl group, an n-propyl group, an n-butyl group, an i-butyl group, a hexyl group, a 2-ethylhexyl group, or C _n H _{2n + 1} (n: 10 to 18). The partition wall paste according to any one of claims 2 to 4, wherein the surfactant has a polar group in the hydrophilic portion. 6. The partition wall paste according to claim 5, wherein the polar group is at least one polar group selected from the group consisting of a carboxyl group, a phosphate group, an amino group and a hydroxyl group. The surfactant is a carboxylic acid or phosphate ester of a polyoxyalkylene alkyl ether represented by the following formula 5 or a salt thereof, an alkyl phosphate ester or a salt thereof, a hydroxyethylalkylamine, a polyoxyalkylenealkylamine, or a polyester. An alkylolamine salt (wherein alkyl is linear or branched alkyl having 8 to 20 carbon atoms, and alkylene is linear or branched alkylene having 2 to 5 carbon atoms). The partition wall paste according to any one of claims 2 to 6.
R ₁ O (R ₂ O) _n X Formula 5
Here, R ₁ is a linear or branched alkyl group having 8 to 20 carbon atoms, R ₂ is an alkylene group having 2 to 5 carbon atoms, n is 1 to 20, and X is a carboxyl group or a phosphate group. 8. The partition wall paste according to claim 1, wherein the polyvinyl butyral has a weight average molecular weight of 20,000 to 130,000. 9. The partition wall paste according to claim 3, wherein the acrylic polymer has a weight average molecular weight of 10,000 to 800,000. The partition wall paste according to any one of claims 1 to 9, wherein the resin contains ethyl cellulose. 11. The partition wall paste according to claim 10, wherein the weight average molecular weight of ethyl cellulose is 50,000 to 200,000. 12. The partition wall paste according to claim 10, wherein a content ratio of ethyl cellulose in 100 parts by mass of the resin is 95 parts by mass or less. As organic solvents, terpineol, ethylene glycol alkyl ether, diethylene glycol monoalkyl ether, ethylene glycol monoalkyl ether acetate, diethylene glycol monoalkyl ether acetate, diethylene glycol dialkyl ether acetate, triethylene glycol alkyl ether acetate, triethylene glycol alkyl ether, propylene glycol alkyl Ether, propylene glycol phenyl ether, dipropylene glycol alkyl ether, tripropylene glycol alkyl ether, propylene glycol alkyl ether acetate, dipropylene glycol alkyl ether acetate, tripropylene glycol alkyl ether acetate, acetate Rutrialkyl citrate, trialkyl citrate, 2,2,4-trimethyl-1,3 pentadiol monoisobutyrate, 2,2,4-trimethyl-1,3 pentadiol diisobutyrate, dimethyl phthalate, phthalate And at least one selected from the group consisting of diethyl acid and dibutyl phthalate (wherein alkyl is methyl, ethyl, propyl, butyl, hexyl, 2-ethylhexyl or phenyl). Item 13. The partition wall paste according to any one of Items 1 to 12. The glass powder is essentially expressed in terms of mol% based on the following oxides:
B ₂ O ₃ 5-80%,
SiO ₂ 0~45%,
ZnO 0-60%,
PbO + Bi ₂ O ₃ 0-70%,
MgO + CaO + SrO + BaO 0-50%,
Li ₂ O + Na ₂ O + K ₂ O 0-30%,
Al ₂ O ₃ + TiO + ZrO ₂ 0-13%,
CuO 0-3%,
SnO ₂ 0-3%,
The partition wall paste according to claim 1, comprising: The glass powder is essentially expressed in terms of mol% based on the following oxides:
B ₂ O ₃ 0-60%,
SiO ₂ 20~65%,
ZnO 0-60%,
PbO + Bi ₂ O ₃ 0-70%,
MgO + CaO + SrO + BaO 0-50%,
Li ₂ O + Na ₂ O + K ₂ O 0-30%,
Al ₂ O ₃ + TiO ₂ + ZrO ₂ 0-13%,
CuO + SnO ₂ + CeO ₂ 0-5%,
The partition wall paste according to claim 1, comprising: A method for producing a plasma display panel having a back substrate, wherein the partition wall paste according to any one of claims 1 to 15 is applied on the glass substrate of the back substrate, and then dried, processed, and fired. A method of manufacturing a plasma display panel, comprising a step of forming partition walls.

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